JP7114860B2 - Photosensitive coloring composition and color filter - Google Patents

Description

The present invention relates to a color liquid crystal display device, a photosensitive coloring composition for a color filter used in the manufacture of a color filter used in a color image pickup tube element, etc., and a color filter having a filter segment formed using the same. It relates to filters.

In a liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of light that has passed through the first polarizing plate, and controls the amount of light that passes through the second polarizing plate. A type that uses a twisted nematic (TN) type liquid crystal is the mainstream. Other representative methods of liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and an electric field is applied in a direction parallel to the substrate, and negative dielectric anisotropy. vertical alignment (VA) method for vertically aligning nematic liquid crystals, and optically convergent bend (OCB) method for optical compensation by making the optical axes of uniaxial retardation films orthogonal to each other. etc., and each has been put to practical use.

Liquid crystal display devices are capable of color display by providing a color filter between two polarizing plates. Demand for higher grades is increasing.

A color filter consists of two or more fine stripe-shaped filter segments of different hues arranged in parallel or crossing on the surface of a transparent substrate such as glass, or fine filter segments arranged in a constant vertical and horizontal arrangement. It consists of those arranged in The filter segments are as fine as several microns to several hundred microns, and are arranged orderly in a predetermined arrangement for each hue.

As a method of forming a color filter, a color resist is formed by mixing and blending a photosensitive agent, an additive, etc. with a resin in which pigment particles, which are a coloring agent, are dispersed. A general method is to form a coating film using a coating apparatus of the above. Then, a method of selectively exposing through a photomask using an aligner or a stepper, developing with an alkaline developer to dissolve and remove unexposed portions, and heat curing to obtain pixels of each color (for example, See Patent Documents 1 and 2.) are known. This is a method of fabricating a color filter by repeating this operation.

Generally, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering. In order to obtain sufficient performance of these transparent electrodes, it is necessary to form them at a high temperature of generally 200° C. or higher, preferably 230° C. or higher. For this reason, currently, a method called a pigment dispersion method using a pigment having excellent heat resistance as a colorant is mainly used as a method for manufacturing a color filter.

Quality items required for color filters include brightness and contrast ratio. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed. state), the transmitted light is attenuated, resulting in a blurry screen. Therefore, in order to realize a high-quality liquid crystal display device, it is essential to increase the contrast.

In addition, if a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. To make the screen bright, it is necessary to increase the number of backlights, which are light sources. Therefore, from the viewpoint of suppressing an increase in power consumption, there is a trend toward increasing the brightness of color filters. Furthermore, as described above, color liquid crystal devices have come to be used in televisions, personal computer monitors, and the like, and thus there is an increasing demand for high brightness, high contrast, and high reliability of color filters.

In recent years, in order to achieve a high contrast ratio and high brightness that cannot be achieved with pigments, a technique using a dye as a coloring agent has been proposed as in Patent Document 1. However, dyes are generally soluble in solvents and polymers, and in the case of colored compositions using dyes, when forming a color filter, the exposed areas that remain as patterns are peeled off in the process of developing with an alkaline developer. There is a problem.

JP-A-2-144502 JP-A-3-53201

An object of the present invention is to provide a coloring composition for color filters which is excellent in developability and pattern adhesion even when a dye is used as a coloring agent, and which has high brightness and a high contrast ratio.

The present inventors have made intensive studies to solve the above problems, and found that by including a blue dye (A) and a polyfunctional urethane acrylate (D1), high brightness, high contrast ratio, and high The present invention was made based on the discovery of the achievement of developability and pattern adhesion.

That is, the present invention is a photosensitive coloring composition comprising a blue dye (A), a binder resin (B), a photopolymerization initiator (C), and a photopolymerizable monomer (D), wherein the photopolymerization It relates to a photosensitive coloring composition characterized in that the functional monomer (D) contains a polyfunctional urethane acrylate (D1).

The present invention also relates to the photosensitive coloring composition, wherein the blue dye (A) is a triarylmethane dye (A1).

The present invention also relates to the photosensitive coloring composition, wherein the polyfunctional urethane acrylate (D1) contains a compound having three or more photopolymerizable functional groups in one molecule.

Further, according to the present invention, the polyfunctional urethane acrylate (D1) has a number of urethane groups of 1.5 mmol/g or more and a number of double bond groups of 4.0 mmol/g or more. Regarding the composition.

Further, the present invention, the content of the photopolymerizable monomer (D), based on the solid weight of the coloring composition, the photosensitive coloring composition characterized in that 7 to 50% by weight Regarding.

The present invention also relates to the photosensitive coloring composition, wherein the polyfunctional urethane acrylate (D1) has an acid group.

The present invention also relates to a color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition.

The present invention will be described in detail below.
In the present application, when "(meth)acrylate", "(meth)acrylic acid", or "(meth)acrylamide" is indicated, it means "acrylate and/or methacrylate", respectively, unless otherwise specified. shall represent "acrylic acid and/or methacrylic acid" or "acrylamide and/or methacrylamide".

<Blue dye>
Dyes used in the photosensitive coloring composition of the present invention include triarylmethane dyes, flavin dyes, auramine dyes, safranin dyes, phloxine dyes, and methylene blue dyes.
Among them, triarylmethane-based dyes or methylene blue-based dyes are preferably used, and more preferably triarylmethane-based dyes, in terms of good color development.

Among these, those exhibiting blue, purple, magenta, and cyan colors are preferred, and C.I. Dyes classified as I. Basic Blue are preferred.

Specifically, C.I. I. Basic Violet 1 (Methyl Violet), Basic Violet 3 (Crystal Violet), Basic Violet 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), Basic Blue 5 (Basic Cyanine EX), Basic Blue 7 (Victoria Pure Blue BO), Basic Blue 26 (Victoria Blue B conc.), C.I. Examples include I. Basic Green 1 (Brilliant Green GX) and Basic Green 4 (Malachite Green). Among them, C.I. I. Basic Blue 7 is preferably used.

As methylene blue dyes, C.I. I. Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), Basic Blue 25 (Basic Blue GO), Basic Blue 24 (New Methylene Blue NX) and the like.

Further, the triarylmethane-based dye will be described in detail below.
<Triarylmethane dye>
A triarylmethane-based dye develops color when an NH ₂ or OH group positioned para to the central carbon takes a quinone structure through oxidation.
They are classified into the following three types depending on the number of NH ₂ and OH groups. Among them, triaminoarylmethane-based dyes are preferred in terms of developing good blue, red and green colors.
a) diaminotriarylmethane dyes b) triaminotriarylmethane dyes c) rosolic acid dyes having an OH group It is preferable because it has excellent sunlight fastness. Further, diphenylnaphthylmethane dyes and/or triarylmethane dyes are preferred.

Blue triarylmethane dyes have spectral characteristics with high transmittance at 400 to 440 nm.

That is, triarylmethane-based basic dyes and methylene blue-based basic dyes are preferred, and specifically, C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 9 (Methylene Blue FZ, Methylene Blue B), 24 (New Methylene Blue NX), 25 (Basic Blue GO) and 26 (Victoria Blue B conc.).

A safranin-based basic dye or a phloxine-based basic dye that exhibits a red or magenta color can also be used as a complementary color of the blue pixel.

<Other coloring agents>
The coloring composition for color filters of the present invention can further contain other coloring agents in addition to the blue dye (A). Other coloring agents are preferably blue pigments, purple pigments or dyes, and red dyes.

When other colorants are contained, the content of the other colorants is preferably 1 to 300 parts by weight per 100 parts by weight of the blue dye (A). More preferably 25 to 200 parts by weight, still more preferably 50 to 100 parts by weight. When the amount of the other coloring agent added is 1 part by weight or more and 300 parts by weight or less, the reproducible chromaticity range is widened, which is preferable.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, more preferably C.I. I. Pigment Blue 15:6.

In particular, when the colored composition is used for the blue filter segment, by using a blue pigment in combination, the spectral spectrum has a high transmittance in the vicinity of 425 to 500 nm, which has a characteristic peak that many backlights have. It is preferable because it is possible to obtain a higher brightness as a blue filter segment than a coloring agent combining a conventional blue pigment and other pigments.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

As a purple dye, C.I. I. acid violet 1, 2, 3, 4, 5, 5:1, 6, 7, 7:1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. are mentioned.
Also, C.I. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, etc. can also be used.

Examples of red dyes include C.I. I. acid red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like.
Also, C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. can also be used.

As a combination of colorants, for example, C.I. I. Pigment Blue 15:6/C.I. I. Pigment Violet 23, C.I. I. Pigment Blue 15:3/C.I. I. Pigment Violet 23, C.I. I. Pigment Blue 15:6/C.I. I. Pigment Violet 23/C.I. I. Acid Red 289, C.I. I. Pigment Blue 15:6/C.I. I. Pigment Violet 23/C.I. I. Acid Red 52, C.I. I. Pigment Blue 15:6/C.I. I. Acid Red 289, C.I. I. Pigment Blue 15:6/C.I. I. acid red 52, etc., but the effects of the present invention are not limited to these.
Further, in order to achieve both solvent resistance and sensitivity, from the viewpoint of obtaining an appropriate ultraviolet transmittance of the coating film, the ratio of the purple coloring agent or the red coloring agent to the blue coloring agent is 100 parts by weight of the blue coloring agent. , is preferably 120 parts by weight or less, more preferably 100 parts by weight or less.

<Refinement of pigment>
When the coloring agent used in combination with the coloring composition of the present invention is a pigment, it can be made finer by salt milling or the like. The average primary particle size of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse in an organic solvent, and if it is larger than 90 nm, sufficient spectral characteristics may not be obtained. For these reasons, the average primary particle size is more preferably in the range of 10 to 70 nm.

The salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill. This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading to a certain extent. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by weight, most preferably 300 to 1,000 parts by weight, based on 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, most preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

When salt milling the pigment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resins used are preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the above organic solvents. The amount of resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

The content of the coloring agent is preferably in the range of 10 to 45% by weight, more preferably in the range of 15 to 40% by weight, based on the solid content of the coloring composition for color filters. This range is preferable because the color reproducibility is good when the color filter is used in a general film thickness range (approximately 1.0 to 3.0 μm).

<Binder resin>
The coloring composition for color filters of the present invention further contains a binder resin. The binder resin can be used as a binder resin that disperses, dyes, or penetrates the coloring agent.
By containing a resin, the dispersion stability of the coloring composition of the present invention becomes better, and when a colored pixel layer of a color filter is formed using the coloring composition for a color filter, less pigment aggregates and developability , a colored pixel layer having a good pattern shape can be obtained.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength region of 400 to 700 nm in the visible light region.
When used in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. Moreover, in order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali-developable colored resist material, the resin is three-dimensionally crosslinked when exposed to an active energy ray to form a coating film. This is more preferable because it increases the photocuring density and, as a result, leads to an improvement in resistance.

Examples of binder resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Among them, it is preferable to use an acrylic resin.

Examples of alkali-soluble resins obtained by copolymerizing ethylenically unsaturated monomers containing acidic groups include resins having acidic groups such as carboxyl groups and sulfone groups.
Specific examples of alkali-soluble resins include acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, or isobutylene/(anhydrous) maleic acid copolymer and the like. Among them, acrylic resins having acidic groups and at least one resin selected from styrene/styrenesulfonic acid copolymers, particularly acrylic resins having acidic groups are preferably used because of their high heat resistance and transparency.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which ethylenically unsaturated double bonds are introduced by methods (i) and (ii) shown below.

<Method (i)>
As method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers. , The carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to form an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce it.

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. monocarboxylic acids, etc., and these may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group and the like. Moreover, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

As a method analogous to method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

<Method (ii)>
As method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and another unsaturated monobasic acid monomer having a carboxyl group or another monomer is copolymerized. There is a method of reacting the side chain hydroxyl groups of the resulting copolymer with the isocyanate groups of an ethylenically unsaturated monomer having an isocyanate group.

Ethylenically unsaturated monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (Meth)acrylates and hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate can be mentioned, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone , and/or (poly)ester mono(meth)acrylates added with (poly)12-hydroxystearic acid and the like can also be used. 2-Hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred from the viewpoint of suppressing coating film foreign substances.

The ethylenically unsaturated monomer having an isocyanate group includes 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but is limited to these. Alternatively, two or more types can be used in combination.

The weight average molecular weight (Mw) of the resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 6,000 to 80,000, in order to disperse the colorant preferably. Also, the number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and the value of Mw/Mn is preferably 10 or less.

When a resin is used as a photosensitive coloring composition for color filters, it is preferable to use a resin having an acid value of 20 to 300 mgKOH/g from the viewpoint of pigment dispersibility, penetrability, developability and resistance. If the acid value is less than 20 mgKOH/g, the solubility in a developer is poor, making it difficult to form a fine pattern. If it exceeds 300 mgKOH/g, no fine pattern remains.

Examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

Since the resin has good film-forming properties and various resistances, it is preferably used in an amount of 20 parts by weight or more with respect to 100 parts by weight of the colorant. It is preferably used in an amount of 1000 parts by weight or less.

<Photoinitiator>
A photopolymerization initiator is added to the coloring composition of the present invention to cure the composition by ultraviolet irradiation and to form a filter segment by photolithography. can be prepared in the form of

Photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 -[4-(4-morpholinyl)phenyl]-1-butanone, or acetophenone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4' -methyldiphenyl sulfide, or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 -diisopropylthioxanthone or thioxanthone compounds such as 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-( p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6- Bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s- triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4- Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], or oxime ester compounds such as O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; bis(2,4,6 -trimethylbenzoyl)phenylphosphine oxide or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; A carbazole-based compound; an imidazole-based compound; or a titanocene-based compound or the like is used.
These photopolymerization initiators can be used singly or as a mixture of two or more at an arbitrary ratio as required.

The content of the photopolymerization initiator is preferably 2 to 200 parts by weight, more preferably 3 to 150 parts by weight based on 100 parts by weight of the colorant, from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives , naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters , acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3′, or 4,4′ -tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone and the like.
These sensitizers can be used singly or as a mixture of two or more at any ratio as required.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (CMC, 1986), but not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the coloring composition, and from the viewpoint of photocurability and developability, 5 to 50 parts by weight. is more preferable.

<Photopolymerizable monomer>
Photopolymerizable monomers include monomers or oligomers that are cured by ultraviolet rays, heat, or the like to form transparent resins. The photopolymerizable monomer of the present invention is characterized by containing a polyfunctional urethane acrylate (D1). By containing a polyfunctional urethane acrylate, a photosensitive coloring composition having excellent pattern adhesion can be obtained.
The polyfunctional urethane acrylate (D1) can be obtained, for example, by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or reacting a polyfunctional alcohol with a (meth)acrylate having an isocyanate group.

From the viewpoint of high sensitivity, the polyfunctional urethane acrylate (D1) preferably has three or more photopolymerizable functional groups in one molecule.
Polyfunctional urethane acrylate having three or more photopolymerizable functional groups in one molecule, for example, a compound having a hydroxyl group having two or more photopolymerizable functional groups and one hydroxyl group in one molecule, and two or more It can be obtained by reacting a compound having an isocyanate group, or a compound having one photopolymerizable group and one hydroxyl group in one molecule and a compound having three or more isocyanate groups. can.

Moreover, it is preferable to use what has an acid group as polyfunctional urethane acrylate (D1) from a developable viewpoint. A urethane acrylate having an acid group can be obtained, for example, by reacting a (meth)acryloyl group of a polyfunctional urethane acrylate (D1) with a compound having a mercapto group and a carboxyl group, or by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group. It can be obtained by reacting a hydroxy acid.

<(Meth)acrylate having a hydroxyl group>
Examples of (meth)acrylates having a hydroxyl group include compounds having one photopolymerizable group and one hydroxyl group in one molecule such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate;
Compounds having two photopolymerizable groups and one hydroxyl group in one molecule such as trimethylolpropane di(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate;
pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, Compounds having three or more photopolymerizable groups and one hydroxyl group in one molecule such as dipentaerythritol-caprolactone-modified penta (meth) acrylate;
A compound having one photopolymerizable group and two hydroxyl groups in one molecule such as glycerin mono (meth) acrylate;
Examples thereof include compounds having two or more photopolymerizable groups and two hydroxyl groups in one molecule, such as a reaction product of an epoxy group-containing compound and (meth)acrylic acid.

<Polyfunctional isocyanate>
Examples of polyfunctional isocyanates include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and bifunctional or higher isocyanate compounds such as burettes, nurates, and adducts thereof.

Examples of aromatic diisocyanates include 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4 "-triphenylmethane triisocyanate, ω,ω'-diisocyanate-1,3-dimethylbenzene (alias: XDI, m-xylylenediisocyanate), ω,ω'-diisocyanate-1,4-dimethylbenzene (alias: p -xylylene diisocyanate), ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.

Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. , dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI, isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1, 4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane and the like.

Examples of the burette body include a burette body of hexamethylene diisocyanate (product name “Sumidule N-75” manufactured by Sumika Bayer Urethane; product name “Duranate 24A-90CX” manufactured by Asahi Kasei Chemicals).

Nurate bodies include, for example, hexamethylene diisocyanate nurate bodies (product name "Sumidule N-3300", manufactured by Sumika Bayer Urethane Co., Ltd.), isophorone diisocyanate nurate bodies (product name "Desmodur Z-4370", Sumika (manufactured by Bayer Urethane Co., Ltd.), tolylene diisocyanate nurate (product name: "Coronate 2030", manufactured by Nippon Polyurethane Co., Ltd.), and the like.

Examples of adducts include bifunctional or higher isocyanate compounds obtained by reacting the above aromatic isocyanates, aliphatic isocyanates, and/or alicyclic isocyanates with polyfunctional alcohols, such as trimethylolpropane. Hexamethylene diisocyanate adduct (product name “Takenate D-160N”, manufactured by Mitsui Chemicals), trimethylolpropane tolylene diisocyanate adduct (product name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.; product name “Takenate D- 102”, manufactured by Mitsui Chemicals), xylylene diisocyanate adduct of trimethylolpropane (product name “Takenate D-110N”, manufactured by Mitsui Chemicals), isophorone diisocyanate adduct of trimethylolpropane (product name “Takenate D-140N”) , manufactured by Mitsui Chemicals, Inc.) and the like.

<Polyfunctional alcohol>
Polyfunctional alcohols, the reaction with (meth)acrylate having an isocyanate group for obtaining the polyfunctional urethane acrylate (D1), the aromatic isocyanate for obtaining the adduct, aliphatic isocyanate, and / Or it can be used in reaction with an alicyclic isocyanate.
Examples of polyfunctional alcohols include ethylene glycol, propylene glycol diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, 2-methyl-1 ,8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, 1,5 -pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanediol Aliphatic or alicyclic diols such as methanol, tricyclodecanedimethanol, cyclopentadiene dimethanol, dimer diol;
1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 4,4′-methylenediphenol, 4, 4'-(2-norbornylidene)diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, or bisphenols such as bisphenol A and bisphenol F Aromatic diols such as bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to;
1,1,1-trimethylolpropane, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane, 1,1,1-trimethylolhexane, 1,1,1-trimethylolheptane, 1,1,1-trimethyloloctane, 1,1,1-trimethylolnonane, 1,1,1-trimethyloldecane, 1,1,1-trimethylolundecane, 1,1,1-trimethyloldodecane, 1,1,1-trimethyloltridecane, 1,1,1-trimethyloltetradecane, 1,1,1-trimethylolpentadecane, 1,1,1-trimethylolhexadecane, 1,1,1-trimethylolhepta Decane, 1,1,1-trimethylol octadecane, 1,1,1-trimethylol nanodecane, 1,1,1-trimethylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1 , 1,1-trimethylol-tert-nonane, 1,1,1-trimethylol-tert-tridecane, 1,1,1-trimethylol-tert-heptadecane, 1,1,1-trimethylol-2-methyl -hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1, Trimethylol branched alkanes such as 1,1-trimethylolisoheptadecane;
Trimethylolbutene, trimethylolheptene, trimethylolpentene, trimethylolhexene, trimethylolheptene, trimethyloloctene, trimethyloldecene, trimethyloldodecene, trimethyloltridecene, trimethylolpentadecene, trimethylolhexadecene, tri Trifunctional polyols such as metrolheptadecene, trimethyloloctadecene, 1,2,6-butanetriol, 1,2,4-butanetriol and glycerin;
Polyols with tetrafunctional or higher functionality such as pentaerythritol, dipentaerythritol, sorbitol, and xylitol;
Polymeric polyols such as polyester polyols, polycarbonate polyols, polyether polyols and polyurethane polyols can be mentioned. These polyfunctional alcohols may be used singly or in combination of two or more.

<(Meth)acrylate having an isocyanate group>
Examples of (meth)acrylates having an isocyanate group include 2-methacryloyloxyethyl isocyanate (product name “Karenzu MOI”, manufactured by Showa Denko KK) and 2-acryloyloxyethyl isocyanate (product name “Karenzu AOI”, manufactured by Showa Denko KK). A compound having one photopolymerizable group and one isocyanate group in one molecule such as
1,1-(Bisacryloyloxymethyl)ethyl isocyanate (product name: Karenz B
EI", manufactured by Showa Denko Co., Ltd.) having two or more photopolymerizable groups and one isocyanate group in one molecule.

<Compound having a mercapto group and a carboxyl group>
Compounds having a mercapto group and a carboxyl group include thioglycolic acid, 3-mercaptopropionic acid and thiomalic acid.

<Hydroxy acid>
Hydroxy acids include glycolic acid, lactic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, malic acid, citric acid, isocitric acid, citramaric acid, leucic acid, ricinoleic acid, ricineraidic acid, cerebronic acid, Hydroxy acids with one hydroxyl group, such as salicylic acid, creosote acid, vanillic acid, syringic acid, mandelic acid, benzilic acid, atrolactinic acid, melilotic acid, coumaric acid, ferulic acid, and sinapinic acid;
Hydroxy acids having two or more hydroxyl groups such as tartaric acid, mevalonic acid, pantoic acid, shikimic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orceric acid, caffeic acid, and umberic acid.

A hydroxy acid can be obtained by reacting some hydroxyl groups of a polyfunctional alcohol with a polybasic acid anhydride. Examples of the polyfunctional alcohol include those shown above.
The polybasic acid anhydride is not particularly limited as long as it is a compound containing one or more acid anhydride groups in the molecule. For example, succinic anhydride, maleic anhydride, glutaric anhydride, butylsuccinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl Maleic Anhydride, Octyl Maleic Anhydride, Decyl Maleic Anhydride, Dodecyl Maleic Anhydride, Butyl Glutamic Anhydride, Hexyl Glutamic Anhydride, Heptyl Glutamic Anhydride, Octyl Glutamic Anhydride, Decyl Glutamic Anhydride, Dodecyl Glutamic Acid Aliphatic dibasic acid anhydrides such as anhydrides;
Methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hydrogenated methyl nadic anhydride, styrene endostyrene tetrahydro phthalic anhydride, trialkyl tetrahydro Alicyclic dibasic acid anhydrides such as phthalic anhydride;
Tribasic or higher alicyclic polybasic acid anhydrides such as hydrogenated trimellitic anhydride;
aromatic dibasic acid anhydrides such as phthalic anhydride and tetrabromophthalic anhydride;
Tribasic or higher aromatic polybasic acid anhydrides such as trimellitic anhydride can be used.

Photopolymerizable monomers that can be used in the coloring composition of the present invention include, in addition to the above-described polyfunctional urethane acrylate, (meth)acryloyl when reacting polyfunctional isocyanate with (meth)acrylate having a hydroxyl group. A component having a double bond group that was not obtained as a polyfunctional urethane acrylate having a group may be included as another monomer.

The number of urethane groups in the polyfunctional urethane acrylate (D1) is preferably 1.5×10 ⁻³ mol/g or more. More preferably, it is in the range of 1.5×10 ⁻³ mol/g to 4.0×10 ⁻³ mol/g.
This range is preferable from the viewpoint of adhesion to the substrate. In the range exceeding 4.0×10 ⁻³ mol/g, the coloring property deteriorates in the heating process.

Further, the number of double bond groups is preferably 4.0 mmol/g or more from the viewpoint of high exposure sensitivity and excellent shape in the development process. It is more preferably 6.0 mmol/g to 10.0 mmol/g. Within this range, the cure shrinkage is low, which is preferable from the viewpoint of the residual film rate.

The content of the photopolymerizable monomer (D) is preferably 7 to 50% by weight, more preferably 10 to 40% by weight, based on the solid weight of the coloring composition. Within this range, both photosensitivity and curing shrinkage can be achieved, which is preferable from the viewpoint of adhesion.

<Leveling agent>
A leveling agent is preferably added to the coloring composition of the present invention in order to improve the leveling properties of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure in its main chain and a dimethylsiloxane having a polyester structure in its main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

Especially preferred as a leveling agent is a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to the coloring composition, its It is useful that it has the characteristic of low surface tension lowering ability and good wettability to the glass plate despite the low surface tension lowering ability, and it is added in an amount that does not cause defects in the coating film due to bubbling. A substance capable of sufficiently suppressing chargeability can be preferably used. A dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used as a leveling agent having such preferred properties. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane is a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of dimethylpolysiloxane, a terminal modified type in which the terminal is bonded to the terminal of dimethylpolysiloxane, and a dimethylpolysiloxane. It may be of any linear block copolymer type with alternating repeating bonds. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., such as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but not limited to.

Anionic, cationic, nonionic or amphoteric surfactants can be added to the leveling agent as auxiliaries. Two or more kinds of surfactants may be mixed and used.
Examples of anionic surfactants added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and esters.

Cationic surfactants added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate. , polyethylene glycol monolaurate; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based and silicone-based surfactants.

<Antioxidant>
The coloring composition for color filters of the present invention can contain an antioxidant. Antioxidants prevent the photopolymerization initiators and thermosetting compounds contained in the coloring composition for color filters from oxidizing and yellowing due to thermal curing and thermal processes during ITO annealing. can be raised. Therefore, by containing an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and to obtain a high transmittance of the coating film.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function. , phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

Among these antioxidants, from the viewpoint of achieving both transmittance and sensitivity of the coating film, preferred are hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants and sulfur antioxidants. agents. More preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant.

Hindered phenol antioxidants include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di -t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4- nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 2,2'-thio- Bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2' thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl )-propionate, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-butylphenyl)-butane, 2,2′-methylene-bis-(6-(1-methyl -cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro cinnamamide) and the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4 -piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3, 4-butanetetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6 -tetramethyl-4-piperidyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4 -diyl) {(2,2,6,6-tetramethyl-4-piperidyl)imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl)imino}], dimethyl succinate and 1- Polycondensate with (2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine and the like. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

Phosphorus antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecyl phosphite, diphenyltridecylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, 4,4' isopropylidenediphenol alkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris(2 ,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearylpentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonyl phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) Phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2, 4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

Sulfur antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]- o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

As the benzotriazole-based antioxidant, an oligomer-type or polymer-type compound having a benzotriazole structure can be used.

Specific examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2- hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

Triazine antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

Salicylic acid ester-based antioxidants include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like. In addition, oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

The content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid weight of the coloring composition for color filters, because the brightness and sensitivity are good.

<Amine compound>
In addition, the colored composition of the present invention may contain an amine-based compound that acts to reduce dissolved oxygen.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoate. ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine and the like.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, etc., if necessary, in order to assist the curing of the thermosetting resin. Phenol-based resins, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, sulfonic acid-based compounds and the like are effective as curing agents, but are not particularly limited to these. Any curing agent can be used as long as it can react with the . Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6 -methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.) can be used. These may be used individually by 1 type, and may use 2 or more types together.
The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other additive ingredients>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time. In addition, an adhesion improver such as a silane coupling agent may be contained in order to improve adhesion to the transparent substrate.

Storage stabilizers include, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. organic phosphines, phosphites, and the like. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the colorant.

Adhesion improvers include vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane and vinyltrimethoxysilane, (meth)acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β-(3, 4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Silane coupling agents include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.

<Organic solvent>
In the coloring composition of the present invention, a coloring agent is sufficiently dispersed and permeated in a coloring agent carrier, and a filter segment is formed by coating a substrate such as a glass substrate in a dry film thickness of 0.2 to 5 μm. An organic solvent is included to facilitate formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of organic solvents include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. , 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene , o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol Monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol Dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl Cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.
These solvents can be used singly or as a mixture of two or more at any ratio as required.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl are preferred because they have good dispersibility and permeability of coloring agents and good applicability of coloring compositions. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

In addition, since the organic solvent can adjust the viscosity of the coloring composition to an appropriate level and form a filter segment having the desired uniform film thickness, it is used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the coloring agent. is preferred.

<Method for producing colored composition>
The coloring composition for a color filter of the present invention contains a coloring agent containing the dye monomer (A) and the salt-forming compound (B) of the present invention, optionally in a coloring agent carrier comprising the resin and a solvent. In addition, it can be produced by finely dispersing, preferably together with a dispersing aid such as a dye derivative, using various dispersing means such as a three-roll mill, two-roll mill, sand mill, kneader, or attritor.

Further, the coloring composition for a color filter of the present invention is obtained by mixing the dye monomer (A), the salt-forming compound (B), and other coloring agents of the present invention separately dispersed in a coloring agent carrier. can also be manufactured. Further, when the coloring matter monomer (A) and the salt-forming compound (B) of the present invention have high solubility, specifically, they have high solubility in the solvent to be used, and are dissolved by stirring, in a state in which no foreign matter is observed. If there is, there is no need to finely disperse and manufacture as described above.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersing aid such as a pigment derivative, a resin-type dispersant, or a surfactant can be used as appropriate. The dispersing aid is excellent in dispersing the colorant and has a great effect of preventing reaggregation of the colorant after dispersion. When used, a color filter with high spectral transmittance can be obtained.

In the present invention, the dye monomer (A) of the present invention can also serve as a dispersing aid for the pigment used in combination.

Examples of dye derivatives include organic pigments, anthraquinones, acridones or triazines into which a basic substituent, an acidic substituent, or a phthalimidomethyl group optionally having a substituent is introduced. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, etc. can be used, and these are It can be used alone or in combination of two or more.

From the viewpoint of improving dispersibility, the amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more, based on 100% by weight of the coloring agent. From the viewpoint of heat resistance and light resistance, it is preferably 40% by weight or less, most preferably 35% by weight or less, based on 100% by weight of the coloring agent.

The resin-type dispersant has a pigment affinity site that has the property of adsorbing to the colorant and a site that is compatible with the colorant carrier, and adsorbs to the colorant to stabilize dispersion on the colorant carrier. It works. Specific examples of resin-type dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, and salts thereof Oily dispersants such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone Resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphoric acid esters, etc. are used, and these can be used alone or in combination of two or more. It is not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 167 manufactured by BYK-Chemie Japan. , 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116 or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940 manufactured by Nippon Lubrizol 、１６０００、１７０００、１８０００、２００００、２１０００、２４０００、２６０００、２７０００、２８０００、３１８４５、３２０００、３２５００、３２５５０、３３５００、３２６００、３４７５０、３５１００、３６６００、３８５００、４１０００、４１０９０、５３０９５、５５０００、５６０００、７６５００ Etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300 manufactured by BASF Japan Ajinomoto Ajisper PA111, PB711, PB821, PB822, PB824 and the like manufactured by Fine Techno Co., Ltd. can be mentioned.

Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate. , monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; Although they can be mixed and used, they are not necessarily limited to these.

When a resin-type dispersant or surfactant is added, it is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on 100% by weight of the colorant. If the blending amount of the resin-type dispersant or surfactant is less than 0.1% by weight, it is difficult to obtain the effect of addition. may affect

<Removal of coarse particles>
The coloring composition for color filters of the present invention is filtered by means of centrifugal separation, sintered filter, membrane filter or the like to obtain coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more. And it is preferable to remove the mixed dust. Thus, the coloring composition preferably does not substantially contain particles of 0.5 μm or larger. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be explained. The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment.
In addition, the color filter may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment, and the yellow filter segment is formed from the colored composition of the present invention. It can be.

Preferably, at least one blue filter segment is formed using the coloring composition for color filters of the present invention.

Base materials such as transparent substrates constituting color filters include glass plates such as soda-lime glass, low-alkali borosilicate glass, and alkali-free aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. Used. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after panelization.

<Manufacturing method of color filter>
The color filter of the invention can be produced by a printing method or a photolithography method.

Formation of the filter segment by the printing method can be patterned simply by repeating printing and drying of a coloring composition prepared as a printing ink, so it is a low-cost method for producing color filters and is excellent in mass productivity. there is Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted by using a dispersant or an extender.

When the filter segment is formed by photolithography, the colored composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto the transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact or non-contact with this film. After that, the film is immersed in a solvent or an alkaline developer or sprayed with a developer to remove the uncured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to promote polymerization of the colored resist material, heating may be applied as necessary. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the printing method.

At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoaming agent or a surfactant can be added to the developer. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method, etc. in addition to the above methods, and the coloring composition for color filters of the present invention can be used in any of these methods. The electrodeposition method is a method of manufacturing a color filter by using a transparent conductive film formed on a substrate to electrodeposit each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which filter segments are formed in advance on the surface of a removable transfer base sheet, and the filter segments are transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate. As the black matrix, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed can be used, but is not limited to these. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or reflective substrate, and then each color filter segment may be formed. An overcoat film, a transparent conductive film, and the like are formed on the color filter of the present invention, if necessary.

The color filter is attached to the opposing substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, and then the injection port is sealed. A liquid crystal display panel is manufactured by laminating them together.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convened bend (OCB). It can be used in a liquid crystal display mode in which coloration is performed using a color filter such as.

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited by these. In the examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively. "PGMAC" means propylene glycol monomethyl ether acetate.

First, the method for measuring the weight average molecular weight (Mw) of the resin and the acid value of the resin, and the method for calculating the number of urethane groups in the photopolymerizable monomer and the number of double bond groups in the photopolymerizable monomer will be described. .

<Resin weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the resin is measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, using TSK-GELSUPERHZM-N as a column by connecting two columns, and using THF as a solvent. molecular weight.

<Acid value of resin (mgKOH/g)>
The acid value of the resin is a value obtained by converting the measured acid value (mgKOH/g) into solid content based on the potentiometric titration method of JISK0070.

<Number of Urethane Groups in Photopolymerizable Monomer>
The number of urethane groups (mmol/g) of the photopolymerizable monomer is a measure of the number of urethane bonds contained in the molecule, and was calculated as follows.
(Number of urethane groups of photopolymerizable monomer in one molecule)/(Molecular weight of photopolymerizable monomer)
In the case of a mixture, the product sum of the weight ratio of each component and the number of urethane groups is defined as the number of urethane groups in the photopolymerizable monomer in one molecule, and the number average molecular weight is defined as the molecular weight of the photopolymerizable monomer.

<Number of Double Bond Groups in Photopolymerizable Monomer>
The number of double bond groups in the photopolymerizable monomer is a measure of the number of double bonds contained in the molecule,
It was calculated by the following formula.
(Number of carbon-carbon double bonds in one molecule)/(molecular weight of photopolymerizable monomer)
In the case of a mixture, the product sum of the weight ratio of each component and the number of carbon-carbon double bonds is defined as the number of carbon-carbon double bonds in one molecule, and the number average molecular weight is defined as the molecular weight of the photopolymerizable monomer.

Next, the photopolymerizable monomers, resins, colorants, pigment dispersions, and photosensitive green colored compositions used in Examples and Comparative Examples will be described.

<Method for producing photopolymerizable monomer>
(Photopolymerizable monomer (D1-1))
801 g of dipentaerythritol pentaacrylate, 128 g of hexamethylene diisocyanate, 1.0 g of N,N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were placed in a 2-liter four-necked flask and heated at 70° C. for 8 hours. After the reaction, IR analysis confirmed disappearance of absorption of isocyanate.
After cooling to room temperature, 70.3 g of mercaptopropionic acid was added and reacted at a temperature of 50-60° C. for 6 hours to obtain a photopolymerizable monomer (D1-1).
This photopolymerizable monomer (D1-1) had an acid value of 43, a number of urethane groups of 1.53 mmol/g, and a number of double bond groups of 6.88 mmol/g.

(Photopolymerization monomer (D1-2))
416 g of trimethylolpropane adduct of hexamethylene diisocyanate, 584 g of pentaerythritol triacrylate, 1.0 g of N,N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were placed in a 2-liter four-necked flask and heated to 70°C. and a photopolymerizable monomer (D1-2) was obtained.
It was confirmed by IR analysis that no isocyanate group was present in the reaction product.
The number of urethane groups in this photopolymerizable monomer (D1-2) was 3.92 mmol/g, and the number of double bond groups was 5.87 mmol/g.

(Photopolymerizable monomer (D1-3))
862 g of dipentaerythritol pentaacrylate, 138 g of hexamethylene diisocyanate, 1.0 g of N,N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were placed in a 2-liter four-necked flask and heated at 70° C. for 8 hours. A photopolymerizable monomer (D1-3) was obtained by reaction.
It was confirmed by IR analysis that no isocyanate group was present in the reaction product.
The number of urethane groups in this photopolymerizable monomer (D1-3) was 1.64 mmol/g, and the number of double bond groups was 8.22 mmol/g.

(Photopolymerizable monomer (D1-4))
In a 2 L four-necked flask, 632 g of 4-hydroxybutyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) and 368 g of hexamethylene diisocyanate were charged and reacted at 60 ° C. for 8 hours to obtain a photopolymerizable monomer (D1-4 ).
It was confirmed by IR analysis that no isocyanate group was present in the reaction product.
The number of urethane groups in this photopolymerizable monomer (D1-4) was 4.39 mmol/g, and the number of double bond groups was 4.39 mmol/g.

(Photopolymerizable monomer (D1-5))
591 g of Kuraray Polyol P2010 (manufactured by Kuraray Co., Ltd.), 99.3 g of hexamethylene diisocyanate, and 1.0 g of N,N-dimethylbenzylamine were placed in a 2 L four-necked flask and reacted at a temperature of 70° C. for 8 hours. rice field.
After cooling to room temperature, 310 g of dipentaerythritol pentaacrylate and 1.0 g of 4-methoxyphenol were added and reacted at 70° C. for 6 hours to obtain a photopolymerizable monomer (D1-5).
It was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-5) had a urethane group number of 1.18 mmol/g and a double bond group number of 2.96 mmol/g.

(Photopolymerizable monomer (D1-6))
36.7 g of 1,6 hexanediol, 622 g of Kuraray Polyol P2010 (manufactured by Kuraray Co., Ltd.), 157 g of hexamethylene diisocyanate, and 1.0 g of N,N-dimethylbenzylamine were placed in a 2-liter four-necked flask and heated to 70°C. was reacted for 8 hours at a temperature of
After cooling to room temperature, 185 g of pentaerythritol triacrylate and 1.0 g of 4-methoxyphenol were added and reacted at 70° C. for 6 hours to obtain a photopolymerizable monomer (D1-6).
It was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-6) had a number of urethane groups of 1.86 mmol/g and a number of double bond groups of 1.86 mmol/g.

(Photopolymerizable monomer (D1-7))
In a 2 L four-necked flask, 477 g of trimethylolpropane adduct of hexamethylene diisocyanate, 445 g of pentaerythritol triacrylate, 77.7 g of γ-hydroxybutyric acid, 1.0 g of N,N-dimethylbenzylamine, and 4-methoxyphenol. 1.0 g was charged and reacted at a temperature of 70° C. for 8 hours to obtain a photopolymerizable monomer (D1-7).
It was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-7) had an acid value of 42, a number of urethane groups of 4.48 mmol/g, and a number of double bond groups of 4.48 mmol/g.

(Photopolymerizable monomer (D1-8))
241 g of trimethylolpropane and 759 g of acryloyloxyethyl isocyanate were placed in a 2 L four-necked flask and reacted at 60° C. for 8 hours to obtain a photopolymerizable monomer (D1-8).
It was confirmed by IR analysis that no isocyanate group was present in the reaction product.
The number of urethane groups in this photopolymerizable monomer (D1-8) was 5.39 mmol/g, and the number of double bond groups was 5.39 mmol/g.

A list of the photopolymerizable monomers (D1-1 to 8) is shown in Table 1.

Abbreviations in Table 1 are shown below.
HD: 1,6-hexanediol P2010: Kuraray Polyol P2010 (manufactured by Kuraray Co., Ltd.)
TMP: Trimethylolpropane TMP-3HDI: Trimethylolpropane adduct of hexamethylene diisocyanate ("Takenate D-160N" manufactured by Mitsui Chemicals)
PTA: pentaerythritol triacrylate DPPA: dipentaerythritol pentaacrylate 4HBA: 4-hydroxybutyl acrylate TGA: thioglycolic acid γHBA: γ-hydroxybutyric acid AOI: acryloyloxyethyl isocyanate HDI: hexamethylene diisocyanate DMBA: N,N-dimethylbenzyl Amine MQ: 4-methoxyphenol

<Method for producing resin solution>
(Resin solution (B1))
A separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirring device was charged with 70.0 parts of propylene glycol monomethyl ether acetate, heated to 80° C., and the inside of the reaction vessel was replaced with nitrogen. After that, from a dropping tube, 15 parts of styrene, 13.5 parts of methacrylic acid, 30 parts of methyl methacrylate, 17.5 parts of n-butyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. A mixture of 14 parts of Aronix M110) and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours to carry out a polymerization reaction. After completion of dropping, the reaction was continued for 3 hours to obtain an acrylic resin solution having a solid content of 50% by weight.
After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Ether acetate was added to obtain a resin solution (B1).

<Method for producing dispersant>
(Dispersant (DI-1))
50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate and 45.4 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 part of AIBN (azobisisobutyronitrile) was further added and reacted for 12 hours. Solid content measurement confirmed that 95% had reacted. Next, add 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst, and heat at 120°C. was reacted for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the nonvolatile content to 50% to obtain a dispersant (DI-1) having an acid value of 43 and a weight average molecular weight of 9,000.

<Method for producing micronized pigment>
(Refined pigment (PB-1))
C. I. Pigment Blue 15:6 (PB15:6) ("Lionol Blue ES" manufactured by Toyocolor Co., Ltd.) 100 parts, pulverized salt 800 parts, and diethylene glycol 100 parts were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and 70 C. for 12 hours. This mixture was poured into 3000 parts of warm water and stirred for 1 hour while heating to 70°C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent. A modified pigment (PB-1) was obtained. The average primary particle size was 28.3 nm.

ＣｕＰｃは、銅フタロシアニン残基を表す。 <Method for producing dye derivative>
(Dye derivative (PD-1))
After chlorosulfonating 50 parts of copper phthalocyanine as a dye component, it was reacted with 14 parts of N,N-dimethylaminopropylamine as an amine component to obtain a dye derivative (PD-1) having a basic group.

CuPc represents a copper phthalocyanine residue.

<Method for producing dye>
(Dye (DY-1)) (triphenylethane-based salt-forming compound)
C. I. 12 parts of Basic Blue 7 (Tokyo Kasei), 7.4 parts of sodium dodecyl sulfate (Tokyo Kasei), 130 parts of dichloromethane and 200 parts of water were mixed and stirred at room temperature for 2 hours. After that, the organic layer was extracted and washed with water, and the organic layer was concentrated under reduced pressure. Then, it was dried in a vacuum dryer at 60°C to obtain 14.7 parts of DY1. Yield was 84.8%.

<Method for producing pigment dispersion>
(Pigment dispersion (DP-1))
After stirring and mixing the following mixture so as to be uniform, using zirconia beads with a diameter of 0.5 mm, after dispersing for 5 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250MKII"), 5.0 μm Filtration with a filter gave a blue pigment dispersion (DP-1).
The pigment dispersion was adjusted with PGMAc so as to have a solid content of 20% by weight.
Solid weights are shown below.
Finely divided pigment (PB-1): 13.0 parts Dye derivative (PD-1): 1.0 parts Dispersant (DI-1): 6.0 parts

<Method for producing dye solution>
(Dye solution (DD-1))
After stirring and mixing the mixture described below so as to be uniform, the mixture was filtered through a 5.0 μm filter to prepare a dye solution (DD-1).
DY-1: 20.0 parts PGMAC: 80.0 parts

[Example 1]
(Photosensitive coloring composition (RB-1))
The following mixture (500 parts in total) was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to obtain a photosensitive green colored composition (RB-1).
Dye solution (DD-1): 214.3 parts Resin solution (B-1): 205.7 parts Photopolymerizable monomer (D1-1): 15.0 parts Photoinitiator (C-1): 1.0 parts ("Irgacure OXE02" manufactured by BASF)
Organic solvent: 64.0 parts (PGMAC)

[Examples 2 to 15, Comparative Example 1]
(Photosensitive green colored composition (RB-2 to 16))
Photosensitive coloring compositions (RB-2 to 16) were prepared in the same manner as the photosensitive coloring composition (RB-1) except that the types and amounts (parts by weight) shown in Table 1 were changed. Incidentally, Examples 6 to 10 and 12 in this specification are reference examples.

Abbreviations in Table 2 are shown below.
Photopolymerization initiator (C-1): ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
(“Irgacure OXE02” manufactured by BASF)
Photopolymerization initiator (C-2): BASF "Irgacure OXE04"
Photopolymerizable monomer (DHPA): dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)

<Evaluation of photosensitive coloring composition>
Developability evaluation and adhesion evaluation of the photosensitive colored compositions obtained in Examples and Comparative Examples were performed by the following methods.

<Formation of filter segments>
A black matrix is patterned on a glass substrate of 100 mm × 100 mm and 1.1 mm thick, the obtained photosensitive coloring composition is applied on the substrate with a spin coater, and the solvent is removed by drying at 70 ° C. for 20 minutes. Then, a coating film having a film thickness of 3.0 μm was obtained. Next, the film was irradiated with ultraviolet rays of 100 mJ/cm ² through a photomask having a stripe pattern of 10 μm and 20 μm widths using an extra-high pressure mercury lamp to form a filter segment. Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.) was used to determine the film thickness of the coating film.

<Evaluation of developability>
An alkaline developer consisting of 0.15% by weight of sodium carbonate, 0.05% by weight of sodium bicarbonate, 0.1% by weight of an anionic surfactant ("Pelex NBL" manufactured by Kao Corporation), and 99.7% by weight of water. After spray development for 30 seconds and 50 seconds, it was washed with deionized water, and the development state of the non-exposed area was visually observed.
The evaluation was made in the following three stages.
⊚: The uncured portion is developed with a development time of 30 seconds.
◯: The non-cured portion is developed with a development time of 50 seconds.
x: The non-cured portion is not developed even after a development time of 50 seconds.

<Adhesion evaluation>
An alkaline developer consisting of 0.15% by weight of sodium carbonate, 0.05% by weight of sodium bicarbonate, 0.1% by weight of an anionic surfactant ("Pelex NBL" manufactured by Kao Corporation), and 99.7% by weight of water. After spray development for 50 seconds, the film was washed with ion-exchanged water, and 10 μm and 20 μm width stripe pattern portions were observed using a metallurgical microscope “BX60” (manufactured by Olympus System Co., Ltd.).
The evaluation was made in the following three stages.
⊚: No peeling up to 10 μm thin wire.
◯: No peeling up to 20 μm thin wire.
x: 20um thin wire is peeled off.

Table 3 shows the evaluation results.

Blue dye of the present invention (A), a binder resin (B), a photopolymerization initiator (C), and a photosensitive coloring composition containing a photopolymerizable monomer (D), the photopolymerizable monomer A photosensitive coloring composition characterized in that the body (D) contains a polyfunctional urethane acrylate (D1) having a (meth)acryloyl group obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate , the developability was good, and the adhesion was also good.
In particular, when the polyfunctional urethane acrylate (D1) had an acid group, excellent developability was exhibited while maintaining good adhesion.

Moreover, from the above results, it was confirmed that the coloring composition for a color filter of the present invention can provide a color filter having both excellent developability and adhesion.

Claims (6)

A photosensitive coloring composition for a color filter containing a blue dye (A), a binder resin (B), a photopolymerization initiator (C), and a polyfunctional urethane acrylate (D1),
Polyfunctional urethane acrylate (D1) is a urethane acrylate having an acid group,
A photosensitive coloring composition for color filters, wherein the polyfunctional urethane acrylate (D1) has a double bond group number of 4.0 to 6.88 mmol/g. 2. The photosensitive coloring composition for color filters according to claim 1, wherein the blue dye (A) is a triarylmethane dye (A1). 3. The photosensitive coloring composition for color filters according to claim 1, wherein the polyfunctional urethane acrylate (D1) has three or more photopolymerizable functional groups in one molecule. 4. The photosensitive coloring composition for color filters according to any one of 1 to 3, wherein the number of urethane groups in the polyfunctional urethane acrylate (D1) is 1.5 mmol/g or more. The total content of the polyfunctional urethane acrylate (D1) and other monomers and oligomers is 7 to 50% by weight, based on the solid weight of the coloring composition. The photosensitive coloring composition for color filters according to any one of the above items. A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition for a color filter according to any one of claims 1 to 5 .